Process and unit for carrying out a reaction on an organic feed, such as dimerisation or metathesis, in the presence of a polar phase containing a catalyst

ABSTRACT

A process for carrying out a reaction on an organic feed, for example dimerization, co-dimerization, oligomerization or metathesis of olefins, as described in which the catalyst is a catalytic metal compound dissolved in a non-aqueous ionic medium which is not or is only slightly miscible with hydrocarbons. The reaction is carried out in a system comprising at least two treatment loops each comprising at least one reaction zone and at least one zone for separating the organic and polar phases between which the polar medium containing the catalytic metal compound, and the organic phase circulate. Fresh polar phase is injected into the second loop and used polar phase is eliminated from the first loop. The hydrocarbon to be transformed is injected into the first loop and the products are withdrawn from the second loop. The invention also concerns a unit for carrying out the process.

SUMMARY OF THE INVENTION

The present invention relates to an improved two-phase process for carrying out a continuous reaction (such as dimerisation, co-dimerisation, oligomerisation or metathesis of olefins) on an organic feed, using a catalyst which contains at least one catalytic element, dissolved in a non-aqueous ionic medium which is not or is only slightly miscible with the olefins. In other words, it relates to a process for carrying out a two-phase catalyzed reaction. The invention also relates to a unit for carrying out the process.

As described above, a two-phase, homogenoeous system has the advantage of using the catalyst better than using a single-phase, homogeneous system. However, continuous economic implementation of a two-phase system poses a certain number of problems, such as interference with the catalyst and with the polar phase by trace impurities contained in the feeds. Such impurities are water, alcohols, ethers, nitrogen-containing compounds and sulphur-containing compounds. They react with the catalyst-polar phase complex.

The process of the invention consists of circulating a counter-current of feed and polar phase in at least two treatment loops. This results in a pre-treatment of the feed in the first loop by used catalytic composition, i.e., that which has lost the majority of its activity, the used catalytic composition originating from the second loop, and then being withdrawn from the process. This implementation reduces consumption of the catalyst-polar phase system, avoids the need for a section for eliminating the transition element and enables the catalyst to be treated off-site.

The process of the invention is a process for carrying out a reaction on an organic feed, in the presence of a polar phase containing at least one catalytic composition resulting from mixing: at least one non-aqueous ionic medium which is not or is only slightly miscible with the organic phase; at least one compound of a catalytic element; and optionally at least one co-catalyst.

In the process of the invention, the feed to be treated and the non-aqueous medium circulate as a counter-current between at least two treatment loops, each loop comprising at least one reaction zone connected to at least one zone for separating the organic and polar phases, the feed to be treated being supplied to the reaction zone of the first loop and fresh non-aqueous ionic medium, i.e., as yet unused, being introduced to the reaction zone in the second or final loop. The other constituent(s) of the catalytic composition can be introduced to any part of the process. The polar phase separated in the separation zone of the second loop or from each of the subsequent loops is sent to the reaction zone of the first loop or respectively the preceding loop, while the organic phase separated in the separation zone of the first loop or its subsequent loops is sent to the reaction zone of the second loop or respectively its subsequent loop. The organic phase obtained from the separation zone of the final loop and the polar phase obtained from the separation zone of the first loop are withdrawn from the process.

In a preferred variation, a portion of the reaction medium from one reaction zone is withdrawn from one part of said zone for re-injection into said zone.

Advantageously, at least a portion of the polar phase wit from one separation zone of a loop is recycled to the reaction zone of the same loop.

Preferably, said fish non-aqueous ionic medium also comprises at least a portion of at lest one constituent of the catalytic composition. In that case, advantageously, the fresh Don-aqueous ionic medium introduced to part of the final loop also comprises at least one transition element compound.

Preferably again, at least a portion of at least one constituent of the catalytic composition is introduced to part of the reaction zone of the first loop. Again advantageously, fresh co-catalyst is Introduced into the reaction zone of the first loop.

In one implementation of the invention, a fresh catalytic composition comprising fresh non-aqueous ionic medium and at least one transition element compound and optionally at least one co-catalyst are introduced into the reaction zone of the last loop.

In the two-loop implementation illustrated below, the process comprises a first and a second treatment loop, each comprising a reaction zone (respectively A₁ and A₂) connected to a separation zone (respectively B₁ and B₂),

the feed to be treated is supplied to the first reaction zone A₁, also co-catalyst, fresh non-aqueous ionic medium mixed with at least one transition element compound and optionally at least a portion of the catalyst being supplied to the second reaction zone A₂;

the polar phase separated from separation zone B₂ is introduced into the reaction zone A₁, while the organic phase separated in separation zone B₁, is introduced into reaction zone A₂;

the organic phase containing the reaction products separated in separation zone B₂ and the used polar phase separated in separation zone B₁ being withdrawn from the process.

In one implementation, for example, a portion of the reaction medium is withdrawn from the reaction zone of the second loop, cooled and re-injected into that zone.

The non-aqueous ionic medium comprises at least one salt known as a “molten salt” and preferred salts of the invention have general formula Q⁺A⁻ where A⁻ represents a non coordinating or slightly coordinating anion. Preferred compounds are those which can form a liquid salt at low temperature, i.e., below 150° C. and advantageously at most 80° C., preferably below 50° C., for example halogenoaluminates, organohalogenoaluminates, halogenogallates, and organohalogenogallates. Q⁺ represents a quaternary ammonium and/or quaternary phosphonium ion. The quaternary ammonium and/or phosphonium ions preferably have general formulae NR¹R²R³R⁴⁺ and PR¹R²R³R⁴⁺ or general formulae R¹R²N═CR³R⁴⁺ and R¹R²P═CR³R⁴⁺ where R¹, R², R³ and R⁴, which may be identical or different, represent hydrogen with the exception of the cation NH₄ ⁺, and preferably a single substituent represents hydrogen, or hydrocarbyl residues containing 1 to 12 carbon atoms, for example saturated or unsaturated alkyl groups, cycloalkyls or aromatics, aryl or aralkyl groups, containing 1 to 12 carbon atoms. The ammonium and/or phosphonium ions can also be derivatives of nitrogen-containing or phosphorous-containing heterocycles containing 1, 2 or 3 nitrogen and/or phosphorous atoms, with general formulae:

where the cycles are constituted by 4 to 10 atoms, preferably 5 or 6 atoms, R¹ and R² being defined as above. The quaternary ammonium or phosphonium ion can also be a cation with formula:

R¹R²⁺N═CR³—R⁵—R³C═N⁺R¹R²

R¹R²⁺P═CR³—R⁵—R³C═P⁺R¹R²

where R¹, R² and R³, which may be identical or different, arm defined as above and R⁵ represents an alkylene or phenylene residue. The following R¹, R², R³ and R⁴ groups can be mentioned: methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, amyl, methylene, ethylidene, phenyl or benzyl radicals; R⁵ may be a methylene, ethylene, propylene or phenylene group. The ammonium and/or phosphonium cation is preferably selected from the group formed by N-butylpyridiunium, N-ethylpyridinium, 3-butyl-1-methylimidazolium, diethylpyrazolium, 3-ethyl-1-methylimidazolium, pyridinium, trimethylphenylammonium, 3-ethyl-1-methylimidazolium, and tetrabutylphosphonium.

These salts can be used alone or as a mixture. They act as a solvent

For dimerisation, co-dimerisation, or oligomerisation, for example, the polar phase of the invention can also comprise a mixture of at least one lithium halide with at least one hydrocarbylaluminium halide (as described in European patent application EP-A-0 753 346).

In a further implementation, it can comprise a mixture of at least one ammonium halide or quaternary phosphonium halide with at least one aluminium halide and/or at least one hydrocarbylaluminium dihalide (as described in EP-A-0 448 445, French patent FR-A2 2 611 700 and EP-A-0 646 412). Nickel is the preferred catalytic element.

The preferred polar phase of the invention comprises (or advantageously is constituted by) a mixture of at least one aluminium halide or respectively at least one hydrocarbylaluminium halide with at least one quaternary ammonium halide and/or quaternary phosphonium halide, or respectively a lithium halide, and advantageously in a molar ratio of aluminium compound/molten salt which is in the range 1 to 2, preferably 1.1 to 1.6.

The hydrocarbylaluminium halide has general formula Al₂X_(x)R_(6−x)where X is chlorine or bromine, R is an alkyl, cycloalkyl, aryl or aralkyl radical comprising 1 to 10, preferably 2 to 6, carbon atoms, x taking the values 2, 3 or 4. They can be used alone or as a mixture. Examples are alkylaluminium chlorides such as ethylaluminium dichloride, isobutylaluminium dichloride, ethylaluminium sesquichloride and diethylaluminium chloride.

The catalytic element (generally a transition metal from groups 6, 8, 9 or 10) is used in the form of a salt such as a carboxylate, acetylacetonate, chloride, bromide, sulphate, nitrate or complexes which these salts form with phosphines, amines, or nitriles. Other compounds may also be suitable.

The concentration of transition metal compound in the polar phase is advantageously in the range 1 mmole per litre to 500 mmoles per litre, preferably in the range 2 to 300 mmoles per litre.

The invention is not limited to the catalytic compositions described above; other compositions may be suitable for dimerisation, co-dimerisation or oligomerisation.

For metathesis, for example, it is possible to use a composition as described in French patent application FR-A-2 715 328, comprising at least one ammonium halide and/or quaternary phosphonium halide mixed with at least one aluminium halide and at least one organometallic aluminium compound. This latter generally has formula Al₂X_(x)R_(3−x) where R is a linear or branched alkyl radical containing 2 to 8 carbon atoms, X is chlorine or bromine and x equals 1, 2 or 3. The catalytic element is tungsten or molybdenum (group 6).

Other catalyst may be suitable.

More generally, the catalyst selected is that which is suitable for the desired reaction.

The reaction mixture comprises a hydrocarbon phase constitute by reactants, products and inert constituents, and the polar phase contains the dissolved transition metal complex.

The temperatures at which the reaction and separation are carried out are generally substantially identical and are generally in the range −20° C. to +80° C., preferably −10° C. to +60° C. The pressure is sufficient to maintain all of the reactants and constituents of the cuts in the liquid phase, i.e., in the complete absence of a gas phase. The operating conditions are clearly those necessary for carrying out the desired reaction.

The invention also relates to a unit for carrying out the reaction in a non-aqueous ionic medium which is not or is only slightly miscible with olefins, comprising:

at least two reaction zones A₁ and A₂;

at leads two separation zones B₁ and B₂ for separating the hydrocarbon phase from the polar phase, said zones being connected to the reaction zones A₁ and A₂;

at least one conduit 1 for introducing polar phase into reaction zone A₂;

at least one conduit 2 for introducing olefin feed into reaction zone A₁;

at least one conduit 3 for supplying hydrocarbon phase separated in separation zone B₁ to reaction zone A₂;

at least one conduit 4 for withdrawing hydrocarbon phase separated in separation zone B₂;

at least one conduit 5 for sending the polar phase separated in separation zone B₂ to reaction zone A₁;

at least one conduit 6 for withdrawing used polar phase separated in separation zone B₁.

The unit preferably also comprises the following means, taken alone or in combination:

at least one conduit 7 connecting separation zone B₂ to reaction zone A₂ to recycle the polar phase;

at least one conduit 8 for withdrawing a portion of the reaction medium from zone A₂ and re-introducing it to said zone;

at least one conduit 9 for withdrawing a portion of the reaction medium from zone A₁ and reintroducing it to said zone;

at least one conduit 10 connecting separation zone B₁ to zone A₁ for recycling the polar phase;

at least one conduit 11 for introducing the reactants into the unit.

Conduits 8 and 9 advantageously comprise heat exchangers.

BRIEF DESCRIPTION OF THE DRAWING

The process and unit will be better understood from the description of the FIGURE. The FIGURE shows a two-loop embodiment of a unit for carrying out the process.

In the FIGURE, the reaction system comprises two treatment loops I and II constituted by reaction zones A₁and A₂ and separation zones B₁ and B₂. Reaction zones A₁ and A₂ are constituted, for example, by a reactor provided with a mechanical stirring system and cooled externally and/or internally, or a reactor provided with external recirculation with a heat exchanger, or a tube reactor acting as a heat exchanger. Separation zones B₁ and B2 are constituted, for example, by a vertical receptacle the height of which is sufficient to ensure proper decanting of the polar phase. A regulation system ensures that the level of polar phase in the separator is constant. The olefin feed enters loop I and used polar catalytic phase leaves this same loop. Fresh polar catalytic phase enters loop II and the organic phase leaves this same loop.

Thus the olefin(s), pure or mixed with saturated hydrocarbons such as those obtained from refining processes, are continuously introduced into reaction zone A₁ via conduit 2. All or part of a constituent of the catalyst is also introduced into zone A₁ via conduit 11, for example an organohalogenated aluminium compound, pure or diluted by a hydrocarbon (in the case of a dimerisation reaction, for example).

The “used” polar phase contained in separator B₁ is sent to reservoir C₁ via conduit 6 at a rate such that the level in separator B₁ remains stable. The hydrocarbon phase contained in separator B₁ passes into reaction zone A₂ via conduit 3 at the mass flow rate of the feed (full loops, no gas phase). “Fresh” polar phase containing the catalytic element, the nickel salt (for a dimerisation reaction, for example) and contained in reservoir C₂ is introduced into reaction zone A₂ via conduit 1.

The polar phase contained in separator B₂ is taken up by a pump and sent to reaction tone A₁ via conduit 5 at a flow rate such that the level of the polar phase in separator B₂ remains constant. A portion is returned to reactor A₂.

The hydrocarbon phase contained in separator B₂ is withdrawn via conduit 4 at the mass flow rate of the feed (full loops, no gas phase). It contains small quantities of organohalogenated aluminium compound and is treated with anhydrous ammonia then washed with an aqueous caustic soda solution followed by water. It then undergoes fractionation to separate unread hydrocarbons, dimers and co-dimers and higher oligomers. Reactors A₁ and A₂ are provided with external recirculation conduits, respectively 9 and 8, to ensure mixing of the two phases and to eliminate the heat of reaction through exchangers.

EXAMPLES

In the following example, which describes dimerisation of n-butenes contained in a C₄ cut from steam cracking of a naphtha using a nickel compound and aluminium dichloroethyl dissolved in a polar phase constituted by 1-butyl-3-methylimidazoliium chloride and aluminium chloride, illustrates the invention without limiting its scope.

EXAMPLE

The two loops were each constituted by a reactor and an exchanger, the total volume being 500 litres, also a separator. The separator was a cylindrical reservoir 5 metres high and 0.5 metres in diameter.

A C₄ cut constituted by 70% of n-butenes and 2% of isobutene, the remainder being constituted by alkanes, was introduced into the first loop at a flow rate of 3900 kg/hour. A solution of dichloroethylaluminium, 50% by weight in hexane, was also introduced, at a flow rate of 9.6 kg/hour.

A polar phase contained in reservoir C₂ and constituted by 0.577 kg of aluminium chloride, 0.622 kg of butylmethylimidazolium chloride and 50 g of anhydrous nickel chloride (aluminium chloride: imidazolium chloride molar ratio=1.22was introduced into the second loop at a flow rate of 1.25 kg/hour. The temperature of the reaction and separation zones was kept at about 10° C.

The polar phase was taken from separator B₂ and sent to reaction zone A₁. The polar phase which accumulated in separator B₁ was sent to reservoir C₁.

On leaving separator B₂, the effluent passing through conduit 4 was treated with anhydrous ammonia, then with a 20% aqueous caustic soda solution and finally with water. The n-butene conversion was 80%; the products were constituted by 95% of dimers and 5% of trimers.

The example shows that the invention is particularly suitable for continuous transformation of olefins, whether it be by dimerisation, co-dimerisation, or oligomerisation, as shown, or by metathesis, for example. The catalyst are, of course, suitable for carrying out the reaction.

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

The entire disclosure of all applications, patents and publications, cited above, and of corresponding French application No.97/06.571, are hereby incorporated by reference.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. 

What is claimed is:
 1. A process comprising catalytically reacting at least one organic compound constituting all or part of a liquid organic phase, in the presence of a polar liquid phase containing a catalyst composition, wherein: the polar liquid phase containing a catalyst composition results from a mixture of at least one catalyst compound and at least one non-aqueous ionic medium, which is sufficiently immiscible with the organic phase that the polar and organic phases can be separated by decanting, the organic phase and the polar phase are circulated in counter-current contact in at least two treatment loops connected in series, each loop comprising at least one reaction zone containing a reaction medium of the organic and polar phases in contact and connected to the reaction zone, at least one separation zone for separating the organic and polar phases by decanting, a feed containing the organic compound is supplied to the reaction zone of a first treatment loop and the polar phase is supplied to the reaction zone of a second treatment loop, polar phase separated in the separation zone of the second treatment loop is sent to the reaction zone of the first treatment loop, and organic phase separated in the separation zone of the first treatment loop is sent to the reaction zone of the second treatment loop.
 2. The process of claim 1, wherein there are more than two treatment loops connected in series, each loop comprising at least one reaction zone connected to at least one separation zone for separating the organic and polar phases by decanting, a feed containing the organic compounds is supplied to the reaction zone of a first treatment loop and fresh non-aqueous ionic medium as a polar phase is supplied to the reaction zone of the final treatment loop, polar phase separated in the separation zone of the second treatment loop and each subsequent treatment loop is sent to the reaction zone of the first treatment loop or, respectively, each preceding treatment loop, organic phase separated in the separation zone of the first treatment loop or subsequent treatment loops is sent to the reaction zone of the second treatment loop or, respectively, subsequent treatment loop, and organic phase obtained from the separation zone of the final treatment loop and polar phase obtained from the separation zone of the first treatment loop being withdrawn from the process.
 3. The process according to claim 2, in which said fresh non-aqueous ionic medium also comprises at least a portion of the catalyst composition.
 4. The process according to claim 3, in which the fresh non-aqueous ionic medium comprises at least one transition element compound for the catalyst.
 5. The process according to claim 2, in which a polar phase comprising fresh non-aqueous ionic medium and at least one transition element compound in the catalyst composition are introduced into the reaction zone of the last treatment loop.
 6. The process of claim 1, in which a portion of the reaction medium from a reaction zone is withdrawn from one part of said zone for re-injection into said zone.
 7. The process according to claim 1, in which at least a portion of the polar phase withdrawn from one separation zone of a treatment loop is recycled to the reaction zone of the same loop.
 8. The process according to claim 1, in which at least a portion of the catalyst composition is introduced to the reaction zone of the first treatment loop.
 9. The process of claim 8, wherein an organic phase is separated from the separation zone of the second treatment loop and it contains an organohalogenated aluminum compound.
 10. The process of claim 1, wherein: the process consists of two treatment loops, a portion of the catalyst composition is supplied to both reaction zones with the portion of the catalyst composition supplied to the reaction zone of the second treatment loop containing a transition element compound, and the organic phase separated in the separation zone of the second treatment loop and the polar phase separated in the separation zone of the first treatment loop are withdrawn from the process.
 11. The process according to claim 10, in which a portion of the reaction medium is withdrawn from the reaction zone of the second treatment loop, cooled and re-injected into that zone.
 12. The process according to claim 1, in which the non-aqueous ionic medium comprises at least one salt with formula Q⁺A⁻ where Q⁺ is a quaternary ammonium salt or a quaternary phosphonium salt and A⁻ is a coordinating or non-coordinating anion.
 13. The process according to claim 12, in which the anion is selected from the group consisting of halogenoaluminates, organohalogenoaluminates, halogenogallates and organohalogenogallates.
 14. The process according to claim 1, in which the polar phase comprises a mixture of at least one quaternary ammonium halide or quaternary phosphonium halide with at least one aluminum halide and/or at least one hydrocarbylaluminum dihalide.
 15. The process according to claim 1, in which the non-aqueous ionic medium results from mixing at least one lithium halide with at least one hydrocarbylaluminum halide.
 16. The process according to claim 1, in which the polar phase comprises a mixture of at least one aluminum halide or respectively at least one hydrocarbylaluminum halide with at least one quaternary ammonium halide and/or quaternary phosphonium halide, or respectively lithium, in a molar ratio which is in the range of 1 to
 2. 17. The process according to claim 1, in which the catalyst composition contains at least one catalytic element selected from the group consisting of elements from groups 6, 8, 9 and 10 of the periodic table.
 18. The process of claim 1, wherein the at least one organic compound includes an olefin and the process involves dimerisation, co-dimerisation or oligomerisation thereof.
 19. The process according to claim 18, in which the catalyst composition comprises at least one nickel compound, at least one quaternary ammonium halide and/or quaternary phosphonium halide, and at least one aluminum halide and/or at least one hydrocarbylaluminum dihalide.
 20. The process of claim 1, wherein the catalyst composition contains at least two different compounds for providing the catalytic effect.
 21. The precess of claim 1, wherein the catalyst composition comprises as an organohalogenated aluminum compound. 